JP2023134512A - Prepreg, laminate, multilayer printed circuit board, semiconductor package and resin composition, and method of manufacturing prepreg, laminate and multilayer printed circuit board - Google Patents

Abstract

To provide prepreg, laminate, multilayer printed wiring board, and semiconductor package capable of exhibiting high adhesion to conductor, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion, and flame resistance, as well as stable and excellent high frequency characteristics (dielectric properties in high frequency bands), and also, to provide a resin composition capable of providing the prepreg, and further, to provide a method for manufacturing the prepreg, the laminate, and the multilayer printed wiring board.SOLUTION: Prepreg containing a resin composition and a sheet fiber reinforced base material, the amount of outgas generated when heated at a temperature of 163°C for 15 minutes is less than 0.7 mass% of the prepreg as a whole.SELECTED DRAWING: None

Description

The present invention relates to prepregs, laminates, multilayer printed wiring boards, semiconductor packages, resin compositions, and methods for producing prepregs, laminates, and multilayer printed wiring boards.

2. Description of the Related Art The speed and capacity of signals used in mobile communication devices such as mobile phones, their base stations, network infrastructure devices such as servers and routers, and large computers are increasing year by year. Along with this, the printed wiring boards installed in these electronic devices need to be compatible with higher frequencies, and dielectric properties (low dielectric constant and low dielectric loss tangent) (hereinafter referred to as "low permittivity and low dielectric loss tangent") in high frequency bands that make it possible to reduce transmission loss are required. There is a need for substrate materials with excellent high-frequency properties (also referred to as high-frequency properties). In recent years, in addition to the electronic devices mentioned above, new systems that handle high-frequency wireless signals have been developed in the ITS (Intelligent Transport Systems) field (automobiles and transportation systems) and indoor short-range communication fields as applications that handle such high-frequency signals. Practical applications and practical plans are progressing, and it is expected that there will be even greater demand for low transmission loss substrate materials for the printed wiring boards mounted on these devices in the future.

In addition, due to environmental issues in recent years, there has been a demand for mounting electronic components using lead-free solder and flame retardancy using halogen-free solder, so materials for printed wiring boards are required to have higher heat resistance and Flame retardant properties are required.

Conventionally, polyphenylene ether (PPE)-based resins have been used as heat-resistant thermoplastic polymers with excellent high frequency characteristics in printed wiring boards that require low transmission loss. For example, a method of using polyphenylene ether and a thermosetting resin in combination has been proposed. Specifically, resin compositions containing polyphenylene ether and epoxy resin (see, for example, Patent Document 1), resin compositions containing polyphenylene ether and cyanate resin, which has a low dielectric constant among thermosetting resins (for example, see Patent Document 1), (see Document 2), etc. are disclosed.

However, the resin compositions described in Patent Documents 1 and 2 have insufficient high-frequency properties in the GHz region, adhesion to conductors, low coefficient of thermal expansion, and flame retardancy, or have poor heat resistance with polyphenylene ether. Low compatibility with the curable resin may result in a decrease in heat resistance.

In order to solve such problems, the present inventors also developed a semi-interpenetrating network (IPN) at the production stage (A stage stage) of a resin composition containing an organic solvent based on polyphenylene ether resin and polybutadiene resin. proposed a resin composition (for example, see Patent Document 3) that can improve compatibility, heat resistance, low coefficient of thermal expansion, adhesion to conductors, etc. by However, in recent years, substrate materials for printed wiring boards have been required not only to support high frequencies but also to have high density, high reliability, and environmental friendliness. There are continuing needs for glass transition temperature, high flame retardancy, etc.

In addition, substrate materials for printed wiring boards used in network-related equipment such as servers and routers must be multilayered due to higher density, and require high reflow heat resistance and through-hole reliability. has been done. Furthermore, as for high frequency characteristics, excellent dielectric properties are required in higher frequency bands, and in general, the dielectric loss tangent of substrate materials tends to increase as the frequency increases. There is an increasing need to exhibit excellent dielectric properties in the 10 GHz band or higher, rather than in dielectric properties at 10 GHz.

In order to solve such problems, the present inventors also achieved good compatibility by blending a polyphenylene ether derivative with a specific molecular structure, a specific thermosetting resin, and a styrene-based thermoplastic elastomer. We have proposed a resin composition (see Patent Document 4) that can exhibit high frequency characteristics, high heat resistance, high adhesion to conductors, low thermal expansion characteristics, high flame retardancy, etc.

Japanese Unexamined Patent Publication No. 58-069046 Special Publication No. 61-018937 Japanese Patent Application Publication No. 2008-95061 International Publication No. 2016/175326

However, as a result of intensive studies by the present inventors, even when conventional resin compositions are used, the results may be lower than the expected high frequency characteristics, and stable and excellent high frequency characteristics may not be achieved. There was a need to develop a resin composition that exhibits this effect.
In view of the current situation, the present invention provides high adhesion with conductors, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion and flame retardancy, as well as stable and excellent high frequency properties (in high frequency bands). To provide a prepreg, a laminate, a multilayer printed wiring board, and a semiconductor package that can exhibit the dielectric properties of An object of the present invention is to provide a method for manufacturing a wiring board.

As a result of intensive research in order to solve the above problems, the present inventors have found that by setting the solid content concentration to a predetermined value in a resin composition containing a polyphenylene ether derivative having a specific molecular structure and an organic solvent, , discovered that it stably exhibits excellent high frequency characteristics while having high adhesion with conductors, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion, and flame retardancy, and completed the present invention. It's arrived.

That is, the present invention relates to the following [1] to [19].
[1] A prepreg containing a resin composition and a sheet-like fiber-reinforced base material,
A prepreg in which the amount of outgas generated when heated at a temperature of 163° C. for 15 minutes is less than 0.7% by mass based on the entire prepreg.
[2] The prepreg according to [1] above, wherein the resin composition contains a polyphenylene ether derivative (A) having an N-substituted maleimide structure-containing group.
[3] The prepreg according to [2] above, wherein the N-substituted maleimide structure-containing group is a group containing a bismaleimide structure in which nitrogen atoms of two maleimide groups are bonded to each other via an organic group.
[4] The resin composition according to [2] or [3] above, wherein the N-substituted maleimide structure-containing group is a group represented by the following general formula (Z).

(In the formula, each R ² is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. y is an integer of 0 to 4. ^{A 1} is represented by the following general formula (II), ( III), (IV) or (V).)

(In the formula, each R ³ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p is an integer of 0 to 4.)

(In the formula, R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 2} is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, single bond, or a group represented by the following general formula (III-1).q and r are each independently an integer of 0 to 4. be.)

(In the formula, R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 3} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. s and t are each independently an integer of 0 to 4.)

(In the formula, n is an integer from 0 to 10.)

(In the formula, R ⁸ and R ⁹ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u is an integer of 1 to 8.)
[5] The resin composition further contains at least one curing accelerator (B) selected from the group consisting of an organic peroxide, an imidazole curing accelerator, and a phosphorus curing accelerator, [1] to The prepreg according to any one of [4].
[6] Any one of the above [1] to [5], wherein the resin composition further contains at least one thermosetting resin (C) selected from the group consisting of an epoxy resin, a cyanate resin, and a maleimide compound. Prepreg as described.
[7] The maleimide compound in the thermosetting resin (C) is a maleimide compound (a) having at least two N-substituted maleimide structure-containing groups and an aminobismaleimide compound represented by the following general formula (VI). (c) The prepreg according to the above [6], containing at least one member selected from the group consisting of:

(In the formula, A ⁴ is the same as the definition of A ¹ in general formula (Z) described in [4] above, and A ⁵ is a group represented by the following general formula (VII).)

(In the formula, R ¹⁷ and R ¹⁸ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. ^{A 8} is an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. 5 alkylene group, alkylidene group having 2 to 5 carbon atoms, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, fluorenylene group, single bond, or the following general formula (VII-1) or (VII-2) ). q' and r' are each independently an integer of 0 to 4.)

(In the formula, R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 9} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- or p-phenylene diisopropylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, or single bond. s' and t' are each independently an integer of 0 to 4.)

(In the formula, R ²¹ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹⁰ and A ¹¹ are each independently an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. w is an integer from 0 to 4.)
[8] A laminate comprising the prepreg according to any one of [1] to [7] above and metal foil.
[9] A multilayer printed wiring board comprising the prepreg according to any one of [1] to [7] above or the laminate according to [8] above.
[10] A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to [9] above.
[11] A resin composition containing a polyphenylene ether derivative (A) having an N-substituted maleimide structure-containing group and an organic solvent, and having a solid content concentration of 50.5% by mass or more.
[12] The resin composition according to [11] above, wherein the polyphenylene ether derivative (A) having an N-substituted maleimide structure-containing group has a structural unit represented by the following general formula (I).

(In the formula, each R ¹ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. x is an integer of 0 to 4.)
[13] The resin composition according to [11] or [12] above, wherein the N-substituted maleimide structure-containing group is a group represented by the following general formula (Z).

(In the formula, each R ² is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. y is an integer of 0 to 4. ^{A 1} is represented by the following general formula (II), ( III), (IV) or (V).)

(In the formula, each R ³ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p is an integer of 0 to 4.)

(In the formula, R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 2} is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, single bond, or a group represented by the following general formula (III-1).q and r are each independently an integer of 0 to 4. be.)

(In the formula, R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 3} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. s and t are each independently an integer of 0 to 4.)

(In the formula, n is an integer from 0 to 10.)

(In the formula, R ⁸ and R ⁹ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u is an integer of 1 to 8.)
[14] Any of the above [11] to [13], further comprising at least one curing accelerator (B) selected from the group consisting of organic peroxides, imidazole-based curing accelerators, and phosphorus-based curing accelerators. The resin composition described in .
[15] The resin composition according to any one of [11] to [14] above, further comprising at least one thermosetting resin (C) selected from the group consisting of epoxy resins, cyanate resins, and maleimide compounds.
[16] A maleimide compound (a) in which the maleimide compound in the thermosetting resin (C) has at least two N-substituted maleimide structure-containing groups and an aminobismaleimide compound represented by the following general formula (VI) The resin composition according to the above [15], containing at least one member selected from the group consisting of (c).

(In the formula, A ⁴ is the same as the definition of A ¹ in general formula (Z) described in [13] above, and A ⁵ is a group represented by the following general formula (VII).)

(In the formula, R ¹⁷ and R ¹⁸ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. ^{A 8} is an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. 5 alkylene group, alkylidene group having 2 to 5 carbon atoms, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, fluorenylene group, single bond, or the following general formula (VII-1) or (VII-2) ). q' and r' are each independently an integer of 0 to 4.)

(In the formula, R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 9} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- or p-phenylene diisopropylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, or single bond. s' and t' are each independently an integer of 0 to 4.)

(In the formula, R ²¹ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹⁰ and A ¹¹ are each independently an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. w is an integer from 0 to 4.)
[17] A method for producing prepreg by impregnating or coating a resin composition on a sheet-like fiber-reinforced base material and drying it to produce a prepreg, the step of producing prepreg so that the amount of outgas of the prepreg satisfies the following conditions ( A method for producing a prepreg, including X).
(Condition of outgas amount)
The amount of outgas generated when heated at a temperature of 163° C. for 15 minutes is less than 0.7% by mass based on the entire prepreg.
[18] A method for producing a laminate, comprising laminating a prepreg obtained by the method for producing a prepreg according to [17] above and a metal foil, and heating and pressurizing the stack by a pressing method.
[19] By subjecting a prepreg obtained by the prepreg manufacturing method described in [17] above or a laminate obtained by the laminate manufacturing method described in [18] above to a circuit forming process and a multilayer adhesive process. , a method for manufacturing a multilayer printed wiring board.

The present invention exhibits high adhesion with conductors, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion and flame retardancy, as well as stable and excellent high frequency properties (dielectric properties in high frequency bands). Prepregs, laminates, multilayer printed wiring boards, and semiconductor packages can be provided. Furthermore, a resin composition capable of providing the prepreg can also be provided. Therefore, the resin composition, prepreg, and laminate can be suitably used for electronic components such as multilayer printed wiring boards and semiconductor packages.
Furthermore, the method for manufacturing a multilayer printed wiring board using the prepreg manufacturing method or the laminate manufacturing method of the present invention provides high adhesion to conductors, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion, and flame retardancy. Furthermore, a multilayer printed wiring board containing a laminate having excellent high frequency properties (dielectric properties in a high frequency band) can be manufactured.

Embodiments of the present invention will be described in detail below. Note that in this specification, a numerical range that is greater than or equal to X and less than or equal to Y (X and Y are real numbers) may be expressed as "X to Y." For example, the description "0.1 to 2" indicates a numerical range of 0.1 or more and 2 or less, and the numerical range includes 0.1, 0.34, 1.03, 2, etc.
In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with the value shown in the Examples. Further, the lower limit value and upper limit value of the numerical range can be arbitrarily combined with the lower limit value or upper limit value of other numerical ranges, respectively.
The present invention also includes embodiments in which the items described in this specification are arbitrarily combined.

[Prepreg]
The present invention is a prepreg containing a resin composition and a sheet-like fiber reinforced base material, which is heated at a temperature of 163° C. for 15 minutes (hereinafter sometimes referred to as "heat treatment for investigating the amount of outgas"). Provided is a prepreg in which the amount of outgas generated when doing so is less than 0.7% by mass (specifically less than 0.70% by mass) based on the entire prepreg. The outgas amount is preferably 0.69% by mass or less, more preferably 0.67% by mass or less, even more preferably 0.65% by mass or less, particularly preferably 0.63% by mass or less, based on the entire prepreg. Most preferably it is 0.61% by mass or less. The lower limit of the amount of outgas is not particularly limited, but is often 0.1% by mass or more, may be 0.3% by mass or more, and may be 0.4% by mass or more. It may be 0.45% by mass or more.
In the present invention, the prepreg is not completely cured (C-staged), but is in a so-called semi-cured (B-staged) state.
Through studies by the present inventors, in order to obtain a laminate that has excellent high frequency properties while having high adhesion with conductors, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion, and good flame retardancy. It was discovered that it is important that the amount of outgas of the prepreg be suppressed to the above-mentioned specific value, leading to the present invention.

One method for reducing the amount of outgassing in the prepreg of the present invention includes (a) a method of adjusting the solid content concentration of the resin composition of the present invention to 50.5% by mass or more; (b) drying conditions during prepreg production. It is preferable to employ at least one selected from the group consisting of these methods.
In addition, in the present invention, the amount of outgas is determined by the mass of the prepreg before heat treatment for investigating the amount of outgas (hereinafter, may be abbreviated as prepreg before heat treatment) and the mass of the prepreg after heat treatment for investigating the amount of outgas (hereinafter, referred to as prepreg before heat treatment). It refers to the mass change rate determined from the mass of (sometimes abbreviated as prepreg after heat treatment), and is calculated by the following formula.
Outgas amount (mass%) = {(mass of prepreg before heat treatment - mass of prepreg after heat treatment) / mass of prepreg before heat treatment} x 100
The outgas components are not particularly limited, but are thought to include at least one selected from the group consisting of organic solvents contained in the resin composition and raw materials mixed in each component of the resin composition. .

(Method for manufacturing prepreg)
The method for producing prepreg of the present invention includes, for example, a method of producing prepreg by impregnating or coating a sheet-like fiber-reinforced base material with a resin composition and drying the prepreg, in which the amount of outgas of the prepreg is "temperature 163. The amount of outgas generated when heated at ℃ for 15 minutes is less than 0.7% by mass based on the resin composition in the prepreg.'' Can be mentioned. The amount of outgas is as explained above.
The step (X) is not particularly limited as long as the outgas amount of the prepreg is within the above range, but for example, (a) the solid content concentration of the resin composition of the present invention is 50.5% by mass or more. Adjusting process [hereinafter sometimes referred to as (a) process. ], (b) step of adjusting drying conditions during prepreg production [hereinafter sometimes referred to as (b) step. ] etc.
The solid content concentration of the resin composition in step (a) will be described later. In the step (b), from the viewpoint of preventing the resin in the resin composition from decomposing, retaining it in B-stage instead of C-stage, and reducing the amount of outgas, for example, it is preferable to is heated and dried at a temperature of 80 to 200°C, more preferably 100 to 180°C, still more preferably 120 to 170°C, preferably 1 to 30 minutes, more preferably 5 to 25 minutes, and even more preferably 10 to 20 minutes. It is preferable to adopt the following drying conditions.
The amount of the resin composition used is such that the solid content derived from the resin composition in the prepreg after drying is 30 to 90% by mass (the remainder corresponds to the content of the sheet-like fiber reinforced base material). Adjustment is preferred. When the solid content derived from the resin composition in the prepreg after drying is within the above range to form a laminate, better moldability tends to be obtained.

As the sheet-like fiber-reinforced base material of the prepreg, known materials used in various laminates for electrically insulating materials can be used. Examples of the material for the sheet-like reinforcing base material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like reinforcing base materials have shapes such as woven fabrics, nonwoven fabrics, raw binders, chopped strand mats, and surfacing mats. Further, the thickness of the sheet-like fiber-reinforced base material is not particularly limited, and for example, a thickness of 0.02 to 0.5 mm can be used. In addition, those that have been surface-treated with a coupling agent or the like and those that have been mechanically opened are preferred from the viewpoints of impregnability of the resin composition, heat resistance when made into a laminate, moisture absorption resistance, and processability. Can be used for
The resin composition contained in the prepreg will be described later.

A solvent method can be employed as a method for impregnating or coating the sheet-like reinforcing base material with the resin composition.
The solvent method is a method in which an organic solvent is contained in a resin composition, a sheet-shaped reinforcing base material is immersed in the resulting resin composition, the sheet-shaped reinforcing base material is impregnated with the resin composition, and then dried. be.

[Resin composition]
The resin composition contained in the prepreg of the present invention is not particularly limited, and known resin compositions used for insulating resin layers of printed wiring boards and the like can be used. Among them, polyphenylene ether derivatives (A) having an N-substituted maleimide structure-containing group are particularly effective from the viewpoints of high adhesion with conductors, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion, flame retardancy, and high frequency properties. Hereinafter, the resin composition may be simply referred to as polyphenylene ether derivative (A) or component (A)].
One preferred embodiment of the resin composition is N- from the viewpoint of obtaining excellent high frequency characteristics while having high adhesion with conductors, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion, and flame retardance. This is a resin composition containing a polyphenylene ether derivative (A) having a substituted maleimide structure-containing group and an organic solvent, and having a solid content concentration of 50.5% by mass or more. When the resin composition of the present invention contains an inorganic filler (D) described below, the solid content concentration referred to herein is a solid content concentration that also includes the inorganic filler.
By setting the solid content concentration of the resin composition to 50.5% by mass or more, results tend to be obtained in which stably excellent high frequency characteristics are obtained compared to the case where the solid content concentration is less than 50.5% by mass. When manufacturing prepreg by impregnating or coating a resin composition onto a sheet-like fiber reinforced base material, it is difficult to work if the resin composition has low fluidity, so generally the solid content concentration is not increased too much. I don't want to. Therefore, the solid content concentration is often adjusted to less than 50.5% by mass. However, when the solid content concentration of the resin composition containing the polyphenylene ether derivative (A) is intentionally increased to the above range, the reduction in the organic solvent remaining in the laminate leads to suppression of the deterioration of high frequency characteristics. There was found.

(Polyphenylene ether derivative (A))
The polyphenylene ether derivative (A) can be used without particular limitation as long as it is a polyphenylene ether derivative having an N-substituted maleimide structure-containing group. The number of N-substituted maleimide structure-containing groups may be at least one.

In particular, since the polyphenylene ether derivative (A) has an N-substituted maleimide structure-containing group, the resin composition has excellent high frequency properties, high adhesion to conductors, high glass transition temperature, low coefficient of thermal expansion, and high flame retardancy. Become a thing. Here, the thermal expansion coefficient as used in the present invention is a value also called a linear expansion coefficient. Further, the N-substituted maleimide structure-containing group is not particularly limited as long as it contains an N-substituted maleimide group.

From the same viewpoint as above, the polyphenylene ether derivative (A) preferably has an N-substituted maleimide structure-containing group and a structural unit represented by the following general formula (I).

(In the formula, each R ¹ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. x is an integer of 0 to 4.)

Examples of the aliphatic hydrocarbon group represented by R ¹ in the general formula (I) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n -pentyl group, etc. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and preferably a methyl group. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. The halogen atom is preferably a fluorine atom from the viewpoint of making it halogen-free (reducing the content of chlorine atoms, bromine atoms, and iodine atoms).
Among the above, R ¹ is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.

x is an integer of 0 to 4, preferably an integer of 0 to 2, and preferably 2. In addition, when x is 1 or 2, R ¹ may be substituted at the ortho position on the benzene ring (however, based on the substitution position of the oxygen atom). Furthermore, when x is 2 or more, the plurality of R ^1s may be the same or different.

Specifically, the structural unit represented by the general formula (I) is preferably a structural unit represented by the following general formula (I').

As the N-substituted maleimide structure-containing group possessed by the polyphenylene ether derivative (A), two maleimide groups are selected from the viewpoints of high frequency properties, adhesion with conductors, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy. A bismaleimide structure in which nitrogen atoms are bonded to each other via an organic group (however, structures derived from this structure are also included. Here, a structure derived from this structure refers to a carbon-carbon double structure possessed by a maleimide group). The group is preferably a group containing a structure in which the bond is reacted with a functional group (such as an amino group). A group represented by the following general formula (Z) is more preferable.

(In the formula, R ² is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. y is an integer of 0 to 4. ^{A 1} is the general formula (II) described below, (III), (IV) or (V).)

The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ² are explained in the same manner as in the case of R ¹ .

y is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0. When y is an integer of 2 or more, the plurality of R ² 's may be the same or different.

The group represented by general formula (II), (III), (IV) or (V) represented by A ¹ is as follows.

(In the formula, each R ³ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p is an integer of 0 to 4.)
The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ³ are explained in the same manner as in the case of R ¹ .

p is an integer of 0 to 4, preferably an integer of 0 to 2 from the viewpoint of availability, more preferably 0 or 1, and even more preferably 0. When p is an integer of 2 or more, the plurality of R ³ 's may be the same or different.

(In the formula, R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 2} is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, single bond, or a group represented by the following general formula (III-1).q and r are each independently an integer of 0 to 4. be.)

The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ⁴ and R ⁵ include the same ones as in the case of R ¹ . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably an ethyl group.

Examples of the alkylene group having 1 to 5 carbon atoms represented by A ² include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc. can be mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of high frequency properties, adhesion with conductors, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy, and methylene groups are preferable. It is more preferable that there be.

Examples of the alkylidene group having 2 to 5 carbon atoms represented by A ² include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, and isopentylidene group. Among these, isopropylidene groups are preferred from the viewpoints of high frequency properties, adhesion to conductors, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy.
Among the above options, A ² is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.

q and r are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 2. When q or r is an integer of 2 or more, the plurality of R ⁴ or R ⁵ may be the same or different.

In addition, the group represented by the general formula (III-1) represented by A ² is as follows.

(In the formula, R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 3} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. s and t are each independently an integer of 0 to 4.)

The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ⁶ and R ⁷ are explained in the same manner as in the case of R ⁴ and R ⁵ .

The alkylene group having 1 to 5 carbon atoms represented by A ³ is the same as the alkylene group having 1 to 5 carbon atoms represented by A ² .
Among the above options, A ³ is preferably an alkylidene group having 2 to 5 carbon atoms.

s and t are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. . When s or t is an integer of 2 or more, the plurality of R ⁶ or R ⁷ may be the same or different.

(In the formula, n is an integer from 0 to 10.)

From the viewpoint of availability, n is preferably 0 to 5, more preferably 0 to 3.

(In the formula, R ⁸ and R ⁹ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u is an integer of 1 to 8.)

The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ⁸ and R ⁹ are explained in the same manner as in the case of R ¹ .
u is an integer of 1 to 8, preferably an integer of 1 to 3, and preferably 1.

As ^A1 in the group represented by the general formula (Z), from the viewpoints of high frequency characteristics, adhesion with conductors, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy, one of the following formulas may be used. A group represented by is preferable.

As ^A1 in the group represented by the general formula (Z), from the viewpoints of high frequency characteristics, adhesion with conductors, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy, one of the following formulas may be used. A group represented by is more preferable.

The polyphenylene ether derivative (A) is preferably a polyphenylene ether derivative represented by the following general formula (A').

(In the formula, A ¹ , R ¹ , R ² , x and y are as defined above. m is an integer of 1 or more.)

m is preferably an integer of 1 to 300, more preferably an integer of 10 to 300, even more preferably an integer of 30 to 200, particularly preferably an integer of 50 to 150.

The polyphenylene ether derivative (A) is preferably a polyphenylene ether derivative represented by any of the following formulas (A'-1) to (A'-4).

(In the formula, m is the same as m in the general formula (A'), and the preferred range is also the same.)

From the viewpoint of low cost raw materials, polyphenylene ether derivatives of the above formula (A'-1) are preferred, and from the viewpoint of excellent dielectric properties and low water absorption, polyphenylene ether derivatives of the above formula (A'-2) are preferred. Polyphenylene ether derivatives are preferable, and from the viewpoint of excellent adhesion with conductors and mechanical properties (elongation, breaking strength, etc.), polyphenylene ethers of the above formula (A'-3) or the above formula (A'-4) Derivatives are preferred. Therefore, depending on the desired characteristics, one type of polyphenylene ether derivative represented by any of the above formulas (A'-1) to (A'-4) may be used alone, or two or more types may be used in combination. can do.

The number average molecular weight of the polyphenylene ether derivative (A) of the present invention is preferably 4,000 to 14,000, more preferably 5,000 to 12,000, and more preferably 7,000 to 12,000. It is more preferably 7,000 to 10,000, particularly preferably 7,000 to 10,000. Further, the number average molecular weight of the polyphenylene ether derivative (A) may be from 4,000 to 8,000, or from 4,000 to 6,500. When the number average molecular weight is 4,000 or more, a better glass transition temperature tends to be obtained in the resin composition of the present invention, prepregs and laminates using the same. Moreover, when the number average molecular weight is 14,000 or less, better moldability tends to be obtained when the resin composition of the present invention is used for a laminate.
In addition, in this specification, the number average molecular weight is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC), and more specifically, the number average molecular weight measurement described in Examples. This is the value obtained using the method.

The content of component (A) in the resin composition of the present invention is not particularly limited, but from the viewpoint of high frequency characteristics etc., it is preferably 1% by mass or more, more preferably 1 to 1% by mass based on the resin composition. The amount is 50% by weight, more preferably 1 to 25% by weight, particularly preferably 1 to 10% by weight.

(Method for producing polyphenylene ether derivative (A))
The polyphenylene ether derivative (A) can be obtained, for example, by the following manufacturing method.
First, an aminophenol compound represented by the following general formula (VIII) [hereinafter referred to as aminophenol compound (VIII)] and, for example, polyphenylene ether having a number average molecular weight of 15,000 to 25,000 are mixed in an organic solvent. By performing a known redistribution reaction, a polyphenylene ether compound (A'') having a primary amino group (hereinafter also simply referred to as a polyphenylene ether compound (A'')) is produced while lowering the molecular weight of the polyphenylene ether. ), and then the polyphenylene ether compound (A'') and a bismaleimide compound represented by general formula (IX) [hereinafter referred to as bismaleimide compound (IX)]. ] The polyphenylene ether derivative (A) can be produced by subjecting it to a Michael addition reaction.

(In the formula, R ² and y are the same as those in the general formula (Z).)

(In the formula, A ¹ is the same as in the general formula (Z) above.)

Examples of the aminophenol compound (VIII) include o-aminophenol, m-aminophenol, p-aminophenol, and the like. Among these, m-aminophenol and p-aminophenol are preferred from the viewpoint of reaction yield when producing the polyphenylene ether compound (A'') and heat resistance when used as a resin composition, prepreg, and laminate. Preferred is p-aminophenol.

The molecular weight of the polyphenylene ether compound (A'') can be controlled by the amount of the aminophenol compound (VIII) used, and the larger the amount of the aminophenol compound (VIII) used, the lower the polyphenylene ether compound (A'') obtained. Molecularized. That is, the amount of the aminophenol compound (VIII) to be used may be adjusted as appropriate so that the number average molecular weight of the polyphenylene ether derivative (A) finally produced falls within a suitable range.

The amount of the aminophenol compound (VIII) to be blended is not particularly limited, but for example, if the number average molecular weight of the polyphenylene ether to be reacted with the aminophenol compound (VIII) is 15,000 to 25,000. By using in the range of 0.5 to 6 parts by mass based on 100 parts by mass of the polyphenylene ether, a polyphenylene ether derivative (A) having a number average molecular weight of 4,000 to 14,000 can be obtained.

The organic solvent used in the manufacturing process of the polyphenylene ether compound (A'') is not particularly limited, but examples include alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone. Ketones such as , methyl isobutyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and mesitylene; Esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate and ethyl acetate; N,N-dimethylformamide, N,N Examples include nitrogen-containing compounds such as -dimethylacetamide and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more. Among these, toluene, xylene, and mesitylene are preferred from the viewpoint of solubility.

Moreover, in the manufacturing process of the polyphenylene ether compound (A''), a reaction catalyst can be used as necessary. As this reaction catalyst, a reaction catalyst used in a known redistribution reaction can be used. For example, from the viewpoint of obtaining a polyphenylene ether compound (A'') with a stable number average molecular weight with good reproducibility, organic peroxides such as t-butylperoxyisopropyl monocarbonate and carboxylic acid metal salts such as manganese naphthenate are used. may be used together. Further, there is no particular restriction on the amount of the reaction catalyst used. For example, from the viewpoint of reaction rate and gelation suppression when producing the polyphenylene ether compound (A''), 0 parts of organic peroxide is added to 100 parts by mass of the polyphenylene ether to be reacted with the aminophenol compound (VIII). The amount may be 0.5 to 5 parts by mass, and the carboxylic acid metal salt may be 0.05 to 0.5 parts by mass.

A predetermined amount of the aminophenol compound (VIII), the polyphenylene ether having a number average molecular weight of 15,000 to 25,000, an organic solvent, and if necessary a reaction catalyst are charged into a reactor, and the reaction is carried out while heating, keeping warm, and stirring to produce polyphenylene. An ether compound (A'') is obtained. For the reaction temperature and reaction time in this step, known reaction conditions for redistribution reactions can be applied.
From the viewpoint of workability and gelation suppression, and from the viewpoint of being able to control the molecular weight of the polyphenylene ether compound (A'') to obtain component (A) with a desired number average molecular weight, for example, the reaction temperature is 70 to 110. The reaction may be carried out at a temperature of 1 to 8 hours.

The solution of the polyphenylene ether compound (A'') produced as described above may be continuously supplied as it is to the next step of producing the polyphenylene ether derivative (A). At this time, the solution of the polyphenylene ether compound (A'') may be cooled or adjusted to the reaction temperature of the next step. Further, as described below, this solution may be concentrated to remove a portion of the organic solvent, or may be diluted by adding an organic solvent, if necessary.

Examples of the bismaleimide compound (IX) used in producing the polyphenylene ether derivative (A) include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl)ether, 3, 3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis(4-(4- maleimidophenoxy)phenyl)propane, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ketone, bis(4-(4-maleimidophenoxy)phenyl)sulfone, 4, Examples include 4'-bis(3-maleimidophenoxy)biphenyl, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, and the like. These may be used alone or in combination of two or more.

Among these, bis(4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide are preferred from the viewpoint of high reaction rate and higher heat resistance. , 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane is preferred.

Bis(4-maleimidophenyl)methane is preferred from the viewpoint that a polyphenylene ether derivative including the polyphenylene ether derivative represented by the formula (A'-1) can be obtained and is inexpensive.
From the viewpoint that a polyphenylene ether derivative including a polyphenylene ether derivative represented by the above formula (A'-2) can be obtained and has excellent dielectric properties and low water absorption, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide is preferred.
2,2- Bis(4-(4-maleimidophenoxy)phenyl)propane and 1,6-bismaleimido-(2,2,4-trimethyl)hexane may also be used.

The amount of bismaleimide compound (IX) used is determined by the amount of aminophenol compound (VIII) used. That is, even if the equivalent ratio (Tb1/Ta1) between the _-NH2 group equivalent (Ta1) of the aminophenol compound (VIII) and the maleimide group equivalent (Tb1) of the bismaleimide compound (IX) is in the range of 2 to 6, It is possible to mix in a range of 2 to 4. By using the bismaleimide compound (IX) within the range of the above equivalent ratio, better heat resistance, higher glass transition temperature, and higher flame retardancy can be obtained in the resin composition, prepreg, and laminate of the present invention. There is a tendency to

A reaction catalyst may be used in the Michael addition reaction when producing the polyphenylene ether derivative (A), if necessary. Usable reaction catalysts include, but are not particularly limited to, acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; and triphenylphosphine. Examples include phosphorus-based catalysts. These may be used alone or in combination of two or more. The amount of the reaction catalyst to be added is not particularly limited, but is preferably 0.01 to 5 parts by weight, for example, based on 100 parts by weight of the polyphenylene ether compound (A'').

The polyphenylene ether derivative (A) is obtained by adding a predetermined amount of the bismaleimide compound (IX) and, if necessary, a reaction catalyst and the like into a polyphenylene ether compound (A'') solution and causing a Michael addition reaction. This step is preferably carried out while heating, keeping warm, and stirring. From the viewpoint of workability and gelation suppression, the reaction conditions are, for example, a reaction temperature of 50 to 160°C and a reaction time of 1 to 10 hours. It is preferable that there be. Further, in this step, the reaction concentration (solid content concentration) and solution viscosity can be adjusted by adding or concentrating an organic solvent as described above. As the organic solvent to be used additionally, the organic solvents exemplified in the manufacturing process of the polyphenylene ether compound (A'') can be applied, and these may be used alone or in combination of two or more. good. Among these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and toluene are preferred from the viewpoint of solubility.

Further, the reaction concentration (solid content concentration) in the manufacturing process of the polyphenylene ether derivative (A) and the polyphenylene ether compound (A'') is not particularly limited, but for example, in any of the manufacturing processes described above, it is 10 to 60% by mass. It is preferably 20 to 50% by mass. When the reaction concentration is 10% by mass or more, the reaction rate does not become too slow and tends to be more advantageous in terms of manufacturing costs. Further, if the reaction concentration is 60% by mass or less, better solubility tends to be obtained. In addition, the solution viscosity is low, stirring efficiency is high, and gelation tends to be less likely.

In addition, after producing the polyphenylene ether derivative (A), from the viewpoint of workability when taking it out from the reactor, and by adding various thermosetting resins etc. to the polyphenylene ether derivative (A), the resin composition of the present invention is prepared. Depending on the usage conditions (for example, solution viscosity and solution concentration suitable for prepreg production), part or all of the organic solvent in the solution may be removed and concentrated as appropriate. It may be diluted by adding. The organic solvent to be added is not particularly limited, and one or more of the organic solvents mentioned above can be used.

The production of the polyphenylene ether compound (A'') and polyphenylene ether derivative (A) obtained by the above manufacturing process can be confirmed by taking out a small amount of sample after each process and performing GPC measurement and IR measurement.
First, the polyphenylene ether compound (A'') has a lower molecular weight than the raw material polyphenylene ether according to GPC measurement, and the peak of the raw material aminophenol compound (VIII) has disappeared, and IR measurement shows that 3. The appearance of primary amino groups of 300 to 3,500 cm ^-1 confirms that the desired polyphenylene ether compound (A'') has been produced. Furthermore, after purification of the polyphenylene ether derivative (A) by reprecipitation, IR measurements showed that the primary amino group peak at 3,300 to 3,500 cm ^-1 disappeared and the peak at 1,700 to 1,730 cm ^-1 disappeared. By confirming the appearance of the peak of the carbonyl group of maleimide, it can be confirmed that the desired polyphenylene ether derivative (A) has been produced.

The resin composition of the present invention has better adhesion to a conductor, thermal expansion coefficient, flame retardancy, and processability than a resin composition containing a polyphenylene ether compound (A'') and component (C) described below. (drilling, cutting).

(organic solvent)
The resin composition of the present invention preferably contains an organic solvent to adjust the solid content concentration to the above range from the viewpoint of dielectric properties, ease of handling, and ease of manufacturing the prepreg described below. .
From the viewpoint of high frequency characteristics, the content of the organic solvent in the resin composition of the present invention is preferably adjusted so that the solid content concentration is 50.5% by mass or more. The solid content concentration of the resin composition is preferably 50.5 to 90% by mass, more preferably 51.0 to 80% by mass, more preferably 53.0 to 80% by mass, and even more preferably 55.0 to 80% by mass. %, particularly preferably from 55.0 to 75% by weight, most preferably from 55.0 to 70.0% by weight. By using a resin composition having a solid content concentration within the above range, excellent high frequency characteristics can be stably expressed, and the good high frequency characteristics can be further improved. In addition, the prepreg is easy to handle, has good impregnability into the base material, has good appearance of the prepreg, and tends to be easy to manufacture with a desired thickness. On the other hand, if the solid content concentration is less than 50.5% by mass, the high frequency characteristics deteriorate slightly, probably because a small amount of the organic solvent in the resin composition remains in the prepreg. In order to meet the recent strong demand for high frequency characteristics, it is important to suppress this deterioration of high frequency characteristics.

Examples of the organic solvent include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; toluene. , xylene, mesitylene, and other aromatic solvents; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethyl sulfoxide; and ester solvents such as γ-butyrolactone. These may be used alone or in combination of two or more. Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, and aromatic solvents are preferred, and aromatic solvents are more preferred. More specifically, propylene glycol monomethyl ether and toluene are preferred.

(Curing accelerator (B))
In addition to the above-mentioned component (A), the resin composition of the present invention includes at least one curing accelerator (B) selected from the group consisting of organic peroxides, imidazole curing accelerators, and phosphorus curing accelerators. [Hereinafter, it may be simply referred to as curing accelerator (B) or component (B). ] It is preferable to contain. By containing component (B), heat resistance etc. can be further improved.

Organic peroxides are not particularly limited, but include, for example, methyl ethyl ketone peroxide, methyl acetoacetate peroxide, acetylacetoperoxide, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t- butyl peroxy)butane, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butyl peroxide) oxy)hexyne, acetyl peroxide, octanoyl peroxide, lauroyl peroxide, benzoyl peroxide, m-tolyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxyisopropyl monocarbonate, 1,1-di(t- hexylperoxy)cyclohexane, t-butylene peroxybenzoate, n-butyl-4,4-di-(t-butylperoxy)-valerate, p-menthane hydroperoxide, diisopropylbenzene, hydroperoxide, 1,1, 3,3-tetramethylbutyl hydroperoxide, cumin hydroperoxide, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5- Di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, di-t-butyl peroxide, bis(1-phenyl-1-methylethyl) peroxide, α,α '-bis(t-butylperoxy)diisopropylbenzene and the like.

From the viewpoint of further improving heat resistance, organic peroxides such as t-butylperoxyisopropyl monocarbonate, 1,1-di(t-hexylperoxy)cyclohexane, and bis(1-phenyl-1-methylethyl)peroxide are used. , diisopropylbenzene hydroperoxide, and α,α'-bis(t-butylperoxy)diisopropylbenzene.

From the viewpoint of storage stability and coatability, the organic oxide preferably has a 1-minute half-life temperature of 140°C or higher, more preferably 160°C or higher. The 1-minute half-life temperature is determined by preparing a 0.1 mol/L organic peroxide solution in a radical-inert solvent such as benzene, and thermally decomposing it in a glass container purged with nitrogen to determine the amount of active oxygen. It is determined by measuring the temperature at which the temperature decreases by half in one minute.

Examples of imidazole-based curing accelerators include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, - Heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl- Examples include 4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline and the like.

From the viewpoint of storage stability of the resin composition, the imidazole curing accelerator is preferably masked imidazole masked with a masking agent. Examples of the masking agent include acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, melamine acrylate, hexamethylene diisocyanate, and the like.

Examples of phosphorus-based curing accelerators include secondary amines such as morpholine, piperidine, pyrrolidine, dimethylamine, diethylamine, dicyclohexylamine, N-alkylarylamine, piperazine, diallylamine, thiazoline, and thiomorpholine; benzyldimethylamine, 2- Tertiary amines such as (dimethylaminomethyl)phenol, 2,4,6-tris(diaminomethyl)phenol; tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium fluoride, chloride Examples include quaternary ammonium salts such as benzalkonium, benzyldi(2-hydroxyethyl)ethylammonium chloride, and decyldi(2-hydroxyethyl)methylammonium bromide.

Component (B) may be used alone or in combination of two or more.

The content ratio of component (B) is not particularly limited, but for example, 100 parts by mass of component (A) of the present invention (however, when using component (C) described below, component (A) and ) The amount is preferably 0.01 to 25 parts by weight, and preferably 0.01 to 20 parts by weight, based on the total of 100 parts by weight of the components. When component (B) is used within such a range, better heat resistance and storage stability tend to be obtained.

(Thermosetting resin (C))
The resin composition of the present invention may contain, as component (C), at least one thermosetting resin selected from the group consisting of epoxy resins, cyanate resins, and maleimide compounds. Note that the maleimide compound does not include the polyphenylene ether derivative (A).

The epoxy resin is preferably an epoxy resin having two or more epoxy groups. Here, the epoxy resin is classified into glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, and the like. Among these, glycidyl ether type epoxy resins may be selected.

Epoxy resins are classified into various epoxy resins depending on the main skeleton, and in each of the above types of epoxy resins, there are also bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc. Epoxy resin; alicyclic epoxy resin; aliphatic chain epoxy resin; novolak epoxy resin such as phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, bisphenol F novolak epoxy resin; phenol aralkyl type epoxy resin; stilbene type epoxy resin; dicyclopentadiene type epoxy resin; naphthalene skeleton-containing type epoxy resin such as naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin; biphenyl type epoxy resin; biphenyl aralkyl type epoxy resin; xylylene type epoxy It is classified into resins; dihydroanthracene type epoxy resins; dicyclopentadiene type epoxy resins, etc.

One type of epoxy resin may be used alone, or two or more types may be used in combination. Among these, naphthalene skeleton-containing epoxy resins and biphenylaralkyl epoxy resins are preferred from the viewpoints of high frequency properties, heat resistance, glass transition temperature, thermal expansion coefficient, flame retardance, and the like.

Moreover, when using an epoxy resin as component (C), a curing agent, a curing aid, etc. for the epoxy resin can be used in combination, if necessary. These are not particularly limited, but include, for example, polyamine compounds such as diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, m-phenylenediamine, and dicyandiamide; bisphenol A, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, and phenol. Examples include polyphenol compounds such as aralkyl resin; acid anhydrides such as phthalic anhydride and pyromellitic anhydride; carboxylic acid compounds; and active ester compounds. These may be used alone or in combination of two or more. The amount used is not particularly limited and can be adjusted as appropriate depending on the purpose. Among these, polyphenol compounds and active ester compounds are preferably used from the viewpoints of heat resistance, glass transition temperature, thermal expansion coefficient, storage stability, and insulation reliability.

Cyanate resins are not particularly limited, but examples include 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)ethane, and bis(3,5-dimethyl-4-cyanato). phenyl)methane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'-bis(4-cyanatophenyl)-m-diisopropyl Examples include benzene, a cyanate compound of a phenol-added dicyclopentadiene polymer, a phenol novolac type cyanate compound, a cresol novolac type cyanate compound, and the like. One type of cyanate resin may be used alone, or two or more types may be used in combination. Among these, 2,2-bis(4-cyanatophenyl)propane is preferably used from the viewpoint of production cost and overall balance of high frequency properties and other properties.

Further, when using a cyanate resin as the component (C), a curing agent, curing aid, etc. for the cyanate resin can be used in combination, if necessary. These include, but are not particularly limited to, monophenol compounds, polyphenol compounds, amine compounds, alcohol compounds, acid anhydrides, carboxylic acid compounds, and the like. These may be used alone or in combination of two or more. The amounts of the curing agent and curing aid used are not particularly limited and can be adjusted as appropriate depending on the purpose. Among these, monophenol compounds are preferably used from the viewpoints of high frequency properties, heat resistance, moisture absorption resistance, and storage stability.

When using a monophenol compound, from the viewpoint of solubility in organic solvents, it is preferable to adopt a method of pre-reacting it and using it as a phenol-modified cyanate prepolymer. The monophenol compound to be used in combination may be blended in its entirety in the prescribed amount at the time of prepolymerization, or may be blended in the prescribed amount before and after prepolymerization, but from the perspective of storage stability, it may be blended separately. This method can be adopted.

The maleimide compound is not particularly limited, but for example, a maleimide compound (a) having at least two N-substituted maleimide structure-containing groups [hereinafter sometimes referred to as component (a)]. ], and an aminobismaleimide compound (c) represented by the following general formula (VI) [hereinafter sometimes referred to as component (c)]. ] at least one of the following. Furthermore, from the viewpoints of solubility in organic solvents, high frequency properties, adhesion with conductors, and moldability of prepregs, the maleimide compound is preferably an aminobismaleimide compound (c).

The aminobismaleimide compound (c) is, for example, a component (a) and an aromatic diamine compound (b) having two primary amino groups [hereinafter sometimes referred to as component (b)]. ] in an organic solvent by Michael addition reaction.

(In the formula, A ⁴ is the same as the definition of A ¹ in the general formula (Z) above, and A ⁵ is a group represented by the following general formula (VII).)

(In the formula, R ¹⁷ and R ¹⁸ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. In the formula, A ⁸ is a carbon number Alkylene group having 1 to 5 carbon atoms, alkylidene group having 2 to 5 carbon atoms, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, fluorenylene group, single bond, or the following general formula (VII-1) or (VII -2). q' and r' are each independently an integer from 0 to 4.)

(In the formula, R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 9} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- or p-phenylene diisopropylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, or single bond. s' and t' are each independently an integer of 0 to 4.)

(In the formula, R ²¹ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹⁰ and A ¹¹ are each independently an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. w is an integer from 0 to 4.)

an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom represented by R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ in the general formula (VII), (VII-1) or (VII-2); Examples include the same ones as R ¹ in general formula (I). The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and preferably a methyl group or an ethyl group.

The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by A ⁸ and A ⁹ in the general formula (VII) or (VII-1), and the alkylidene group having 2 to 5 carbon atoms in the general formula (VII-2) The alkylene group having 1 to 5 carbon atoms represented by A ¹⁰ and A ¹¹ is explained in the same manner as in the case of A ² in the general formula (III).

q' and r' are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, and preferably 0 or 2. s' and t' are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, preferably 0 or 1, and preferably 0. w is an integer of 0 to 4, preferably an integer of 0 to 2, and preferably 0, from the viewpoint of availability.

The component (a) is not particularly limited, and, for example, the same component as the bismaleimide compound (IX) may be used. Component (a) includes, for example, bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl-5, 5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, Bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl)ketone, bis(4-(4-maleimidophenoxy)phenyl)sulfone, 4,4'-bis(3-maleimidophenoxy)biphenyl, 1,6- Examples include bismaleimide-(2,2,4-trimethyl)hexane. Component (a) may be used alone or in combination of two or more depending on the purpose, use, etc. In addition, component (a) is preferably a bismaleimide compound, and from the viewpoint of being inexpensive, bis(4-maleimidophenyl)methane is preferable, and also has excellent dielectric properties and low water absorption. 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide is preferable from the viewpoint of high adhesion to conductors and mechanical properties (elongation, breaking strength, etc.). From the viewpoint of superiority, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane is preferred.

As mentioned above, the aminobismaleimide compound (c) is produced by performing a Michael addition reaction between the component (a) and the aromatic diamine compound (b) having two primary amino groups in an organic solvent. Obtainable.

The component (b) is not particularly limited, but from the viewpoints of high solubility in organic solvents, high reaction rate during synthesis, and high heat resistance, 4,4'-diaminodiphenylmethane is used. , 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane , 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, and the like.
4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-Diamino-3,3'-diethyl-diphenylmethane is preferred. In addition to being excellent in solubility, reaction rate, and heat resistance, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4, 4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline and 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline are preferred. Furthermore, in addition to being excellent in solubility, reaction rate, heat resistance, and adhesion with conductors, 4,4'-[1,3-phenylenebis(1- Preference is given to choosing methylethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline.
One type of these may be used alone or two or more types may be used in combination depending on the purpose, use, etc.

The organic solvent used in producing the aminobismaleimide compound (c) is not particularly limited, but for example, the organic solvents exemplified in the production process of the polyphenylene ether compound (A'') above can be used. These may be used alone or in combination of two or more. Among these, from the viewpoint of solubility, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N,N-dimethylformamide, and N,N-dimethylacetamide are preferable.

The amounts of component (a) and component (b) used when producing component (c) are the -NH2 group equivalent (Ta2) of component (b), the maleimide group equivalent (Tb2) of component (a), The equivalent ratio (Tb2/Ta2) is preferably in the range of 1 to 10, more preferably in the range of 2 to 10. By using components (a) and (b) within the above range, the resin composition, prepreg, and laminate of the present invention can have excellent high frequency properties, high adhesion to conductors, excellent heat resistance, and high Glass transition temperature and high flame retardancy are obtained.

Although it is not necessary to use a reaction catalyst in the Michael addition reaction when producing the aminobismaleimide compound (c), it is also possible to use one if necessary. The reaction catalyst is not particularly limited, but any reaction catalyst that can be used in the Michael addition reaction during the production of the polyphenylene ether derivative (A) described above can be used. As mentioned above, the amount of the reaction catalyst is not particularly limited.

Further, when a maleimide compound is used as the component (C), a curing agent, a crosslinking agent, a curing aid, etc. of the maleimide compound can be used in combination. These include, but are not particularly limited to, styrene monomers, vinyl compounds such as divinylbenzene and divinylbiphenyl; (meth)acrylate compounds; allyl compounds such as triallyl cyanurate and triallyl isocyanurate; diaminodiphenylmethane, etc. Examples include polyamine compounds such as These may be used alone or in combination of two or more. The amounts used are not particularly limited, and can be adjusted as appropriate depending on the purpose. Among these, vinyl compounds and polyamine compounds may be used from the viewpoint of high frequency characteristics, heat resistance, etc.

The aminobismaleimide compound (c) is obtained by charging the above components (a), (b), an organic solvent, and if necessary a reaction catalyst in a reactor, and performing a Michael addition reaction while heating, keeping warm, and stirring. . For reaction conditions such as reaction temperature and reaction time in this step, for example, the reaction conditions used in the Michael addition reaction during the production of the polyphenylene ether derivative (A) described above can be applied.

The reaction concentration (solid content concentration) is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass. When the reaction concentration is 10% by mass or more, the reaction rate does not become too slow and tends to be more advantageous in terms of manufacturing costs. When the amount is 90% by mass or less, better solubility tends to be obtained. In addition, since the solution viscosity is low, stirring efficiency is good and gelation is less likely. After producing the aminobismaleimide compound (c), as in the production of the polyphenylene ether derivative (A), part or all of the organic solvent may be removed (concentrated) or an organic solvent may be added depending on the purpose. It can be diluted.

(Content ratio of component (A) and component (C))
When the resin composition of the present invention contains component (C), there is no particular restriction on the content ratio [(A)/(C)] of the component (A) and component (C), but in terms of mass ratio, It is preferably from 5/95 to 80/20, preferably from 5/95 to 75/25, preferably from 5/95 to 70/30, and preferably from 5/95 to 50/50. Preferably, the ratio is 10/90 to 50/50. When the content ratio of component (A) to the total of components (A) and (C) is 5% by mass or more, better high frequency characteristics and low hygroscopicity tend to be obtained. Further, if it is 80% by mass or less, better heat resistance, better moldability, and better workability tend to be obtained.

The thermosetting resin composition of the present invention may optionally contain an inorganic filler (D) (hereinafter sometimes referred to as component (D)), a flame retardant (E) (hereinafter referred to as component (E)), ) may also be used. By containing these, various properties of a laminate can be further improved. For example, by optionally containing an appropriate inorganic filler in the thermosetting resin composition of the present invention, low thermal expansion characteristics, high elastic modulus, heat resistance, flame retardance, etc. can be improved. Furthermore, by containing an appropriate flame retardant, high flame retardance can be imparted while suppressing a decrease in high frequency properties, heat resistance, adhesion to conductors, and glass transition temperature.

(Inorganic filler (D))
Component (D) used in the thermosetting resin composition of the present invention is not particularly limited, but examples include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, titanium Strontium acid, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate , silicon carbide, etc. can be used. These may be used alone or in combination of two or more. Further, there are no particular limitations on the shape and particle size of the inorganic filler, but for example, particle sizes of 0.01 to 20 μm, preferably 0.1 to 10 μm are suitably used. Here, the particle size refers to the average particle size, and refers to the particle size at a point corresponding to 50% of the volume when a cumulative frequency distribution curve based on the particle size is determined with the total volume of the particles as 100%. It can be measured using a particle size distribution measuring device using a laser diffraction scattering method.

When using component (D), the amount used is not particularly limited, but for example, the content ratio of component (D) in the thermosetting resin composition containing component (D) is 3 to 65% by volume. It is preferably 5 to 60 volume %, more preferably 10 to 60 volume %. When the content ratio of component (D) in the entire thermosetting resin composition is within the above range, good curability, moldability, and chemical resistance can be obtained. Moreover, when using component (D), it is preferable to use a coupling agent in combination for the purpose of improving the dispersibility of component (D) and the adhesion between component (D) and the organic component in the resin composition. The coupling agent is not particularly limited, and for example, various silane coupling agents and titanate coupling agents can be used. These may be used alone or in combination of two or more. Further, the amount used is not particularly limited, and is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, per 100 parts by weight of component (D) used. More preferred. Within this range, there is little deterioration in various properties, and the advantages of using the above-mentioned component (D) can be effectively exhibited. When using a coupling agent, the coupling agent is directly added to the inorganic filler in advance by a dry method, rather than the so-called integral blend processing method in which the coupling agent is added after blending component (D) into the resin composition. Alternatively, a method using an inorganic filler that has been surface-treated in a wet manner is preferable. By using this method, the characteristics of the component (D) can be more effectively exhibited.

When using component (D) in the present invention, in order to improve the dispersibility of component (D) in the thermosetting resin composition, if necessary, component (D) may be prepared in a slurry in which component (D) is previously dispersed in an organic solvent. It is more preferable to use it as The organic solvent used in slurrying the component (D) is not particularly limited, but the organic solvents exemplified in the above-mentioned process for producing the polyphenylene ether compound (A') can be used. These may be used alone or in combination of two or more. Moreover, among these, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferable from the viewpoint of dispersibility. Further, the nonvolatile content concentration of the slurry is not particularly limited, but for example, from the viewpoint of sedimentation and dispersibility of the inorganic filler, it is preferably 50 to 80% by mass, more preferably 60 to 80% by mass.

(Flame retardant (E))
The resin composition of the present invention may contain a flame retardant (E).
Component (E) includes phosphorus flame retardants, metal hydrates, halogen flame retardants, and the like. From the viewpoint of environmental issues, component (E) is preferably at least one selected from the group consisting of phosphorus-based flame retardants and metal hydrates, and it is preferable to use phosphorus-based flame retardants and metal hydrates together. More preferred. The flame retardant (E) may be used alone or in combination of two or more.

-Phosphorous flame retardant-
The phosphorus-based flame retardant is not particularly limited as long as it contains a phosphorus atom among those commonly used as flame retardants.Inorganic phosphorus-based flame retardants are also preferable, and organic It is also preferable that the flame retardant is a phosphorus-based flame retardant. Note that from the viewpoint of environmental issues, one that does not contain halogen atoms can be selected. From the viewpoints of high frequency properties, adhesion to conductors, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy, organic phosphorus-based flame retardants are preferred.

Examples of inorganic phosphorus flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide; ; phosphoric acid; phosphine oxide and the like.

Examples of organic phosphorus flame retardants include aromatic phosphoric acid esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic esters, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, etc. can be mentioned. Among these, aromatic phosphoric acid ester compounds and metal salts of disubstituted phosphinic acids can be selected. Here, the metal salt is preferably any one of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, and zinc salt, and preferably aluminum salt.
Further, among the organic phosphorus-based flame retardants, aromatic phosphate esters can be selected.

Examples of aromatic phosphate esters include triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 1,3 -phenylene bis(di-2,6-xylenyl phosphate), bisphenol A-bis(diphenyl phosphate), 1,3-phenylene bis(diphenyl phosphate) and the like.

Examples of monosubstituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate, and the like.
Examples of the 2-substituted phosphinate include phenyl diphenylphosphinate, methyl diphenylphosphinate, and the like.
Examples of metal salts of di-substituted phosphinic acids include metal salts of dialkylphosphinic acid, metal salts of diallylphosphinic acid, metal salts of divinylphosphinic acid, metal salts of diarylphosphinic acid, and the like. These metal salts are preferably lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, or zinc salts, and aluminum salts are more preferable.

Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; and melam polyphosphate.

Examples of the cyclic organic phosphorus compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10- Examples include phosphaphenanthrene-10-oxide.

Among these, at least one selected from the group consisting of aromatic phosphoric acid esters, metal salts of disubstituted phosphinic acids, and cyclic organic phosphorus compounds is preferable; It is more preferable to use at least one kind selected from the group consisting of: It is even more preferable to use a metal salt of a disubstituted phosphinic acid and a cyclic organic phosphorus compound in combination. In particular, the metal salt of the disubstituted phosphinic acid is preferably a metal salt of dialkylphosphinic acid, and more preferably an aluminum salt of dialkylphosphinic acid. The cyclic organic phosphorus compound is preferably 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

In addition, when a metal salt of a disubstituted phosphinic acid and a cyclic organophosphorus compound are used together, the content ratio of the metal salt of a disubstituted phosphinic acid to the cyclic organophosphorus compound [metal salt of a disubstituted phosphinic acid/cyclic organophosphorus compound] is as follows: The mass ratio is preferably 0.6 to 2.5, preferably 0.9 to 2, preferably 1 to 2, and preferably 1.2 to 2.

Further, the aromatic phosphoric acid ester is preferably an aromatic phosphoric acid ester represented by the following general formula (E-1) or (E-2), and the metal salt of the disubstituted phosphinic acid is A metal salt of a disubstituted phosphinic acid represented by the general formula (E-3) is preferred.

(In the formula, R ^E1 to R ^E5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. e and f are each independently an integer of 0 to 5, g, h and i is each independently an integer from 0 to 4.
R ^E6 and R ^E7 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. M is a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom, or a zinc atom. m1 is an integer from 1 to 4. )

The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^E1 to R ^E5 include the same ones as for R ¹ in the general formula (I).

e and f are preferably integers from 0 to 2, and preferably 2. g, h and i are preferably integers of 0 to 2, preferably 0 or 1, and preferably 0.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^E6 and R ^E7 include the same ones as for R ¹ in the above general formula (I). The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and preferably an ethyl group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ^E6 and R ^E7 include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and the like. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.

m1 represents the valence of the metal ion, that is, it changes within the range of 1 to 4 depending on the type of M.
M is preferably an aluminum atom. Note that when M is an aluminum atom, m1 is 3.

-Metal hydrate-
Examples of the metal hydrate include aluminum hydroxide hydrate, magnesium hydroxide hydrate, and the like. These may be used alone or in combination of two or more. The metal hydroxide can also be considered an inorganic filler, but if it is a material that can impart flame retardancy, it is classified as a flame retardant.

-Halogen flame retardant-
Examples of the halogen flame retardant include chlorine flame retardants, bromine flame retardants, and the like. Examples of chlorinated flame retardants include chlorinated paraffin. Examples of brominated flame retardants include brominated epoxy resins such as brominated bisphenol A type epoxy resins and brominated phenol novolac type epoxy resins; hexabromobenzene, pentabromotoluene, ethylene bis (pentabromophenyl), and ethylene bis tetra Bromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, 2, Bromine-added flame retardants such as 4,6-tris(tribromophenoxy)-1,3,5-triazine (here, "additive" refers to bromine introduced into the polymer in a form that is not chemically bonded). ); tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, brominated styrene, etc. Examples include brominated reactive flame retardants containing a bonding group (here, "reactive type" refers to those in which bromine is introduced into a polymer in a chemically bonded form). These may be used alone or in combination of two or more.

(Content ratio of component (E))
When the resin composition of the present invention contains a phosphorus flame retardant, the content ratio of the phosphorus flame retardant in the resin composition of the present invention is not particularly limited. The content of phosphorus atoms in the total amount of other components (excluding component (D)) is preferably 0.2 to 5% by mass, more preferably 0.3 to 3% by mass. When the content of phosphorus atoms is 0.2% by mass or more, better flame retardance tends to be obtained. Moreover, when the content of phosphorus atoms is 5% by mass or less, better moldability, high adhesion with conductors, excellent heat resistance, and high glass transition temperature tend to be obtained.

On the other hand, when a halogen flame retardant is contained in the resin composition of the present invention, the content should be 100 parts by mass (however, When component (C) is not used, the amount is preferably 20 parts by mass or less, preferably 10 parts by mass or less, and preferably 5 parts by mass or less based on 100 parts by mass of component (A). .

In addition, when the resin composition of the present invention contains a flame retardant other than a phosphorus-based flame retardant and a halogen-based flame retardant, the total amount of components (A) and (C) is 100 parts by mass, although it is not particularly limited. (However, if component (C) is not used, the amount is preferably 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, and preferably 1 to 15 parts by weight, based on 100 parts by weight of component (A)). The amount is preferably 10 parts by weight, and preferably 1 to 6 parts by weight.

(Flame retardant aid)
The resin composition of the present invention can contain a flame retardant aid. As the flame retardant aid, for example, inorganic flame retardant aids such as antimony trioxide and zinc molybdate can be used.

When a flame retardant aid is contained in the resin composition of the present invention, its content ratio is not particularly limited, but for example, the total of component (A) and component (C) is 100 parts by mass (however, (C When component ) is not used, the amount is preferably 0.1 to 20 parts by weight, and preferably 0.1 to 10 parts by weight, based on 100 parts by weight of component (A). When the flame retardant aid is used within this range, better chemical resistance tends to be obtained.

The resin composition of the present invention may contain coupling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, etc., selected as appropriate. can. These may be used alone or in combination of two or more. Furthermore, the amounts used are not particularly limited.
Note that, although not particularly limited, one embodiment of the resin composition of the present invention includes an embodiment that does not substantially contain a thermoplastic elastomer. Here, "substantially not containing" means 0 parts by mass, not containing it at all, or to such an extent that there is no essential meaning in containing it (for example, in the case of thermoplastic elastomers, 1 part by mass or less, 0 parts by mass or less). .5 parts by mass or less). Examples of the thermoplastic elastomer include styrene elastomer, olefin elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, acrylic elastomer, silicone elastomer, and derivatives thereof.

(Method for manufacturing resin composition)
A resin composition can be produced by mixing the component (A), the component (B), the component (C), other components, an organic solvent, etc. contained as necessary by a known method. At this time, it may be dissolved or dispersed while stirring. Conditions such as the mixing order and the temperature and time during mixing and stirring are not particularly limited and can be arbitrarily set.
As mentioned above, when producing the resin composition of the present invention, by adjusting the solid content concentration of the resin composition within the above range, it tends to be easier to obtain a laminate having particularly excellent high frequency characteristics. Therefore, in the method for producing a resin composition, "the solid content concentration of the resin composition containing the polyphenylene ether derivative (A) having an N-substituted maleimide structure-containing group and an organic solvent is adjusted to 50.5% by mass or more. , a solid content concentration adjustment step. The resin composition used in the solid content concentration adjustment step is as described above regarding the resin composition.

(physical properties or characteristics)
When a laminate is produced from the resin composition of the present invention, the glass transition temperature of the cured product of the resin composition is not particularly limited. From the viewpoint of excellent processability, the glass transition temperature of the resin composition after curing is preferably 150°C or higher, more preferably 160°C or higher, even more preferably 170°C or higher, The temperature is particularly preferably 180°C or higher, and most preferably 200°C or higher. Although there is no particular upper limit to the glass transition temperature, for example, it is preferably 1,000°C or lower, preferably 500°C or lower, and preferably 300°C or lower.

Further, when a laminate is produced from the resin composition of the present invention, the coefficient of thermal expansion (Z direction, Tg or less) of the cured product of the resin composition is not particularly limited, but from the viewpoint of suppressing warpage of the laminate, It is preferably 57 ppm/°C or less, more preferably 50 ppm/°C or less, even more preferably 45 ppm/°C or less, and particularly preferably 40 ppm/°C or less. There is no limit to the lower limit of the thermal expansion coefficient, but it is, for example, 25 ppm/°C or more.
Note that the glass transition temperature and thermal expansion coefficient are values measured according to the IPC standard, as described in Examples.

When a laminate is produced from the resin composition of the present invention, the dielectric constant and dielectric loss tangent of the cured resin composition are not particularly limited, but from the viewpoint of suitability for use in a high frequency band, the dielectric constant at 10 GHz should be small. is preferable, specifically, it is preferably 3.85 or less, more preferably 3.70 or less, and even more preferably 3.60 or less. The lower limit of the dielectric constant is not particularly limited, but is, for example, 0.5 or more, may be 1.0 or more, 3.0 or more, or 3.4 or more.

Further, the dielectric loss tangent at 10 GHz is preferably small, specifically, preferably 0.007 or less, more preferably 0.006 or less, and even more preferably 0.0055 or less. The lower limit of the dielectric loss tangent is not particularly limited, and the smaller the better, but for example, it is 0.0001 or more, may be 0.0020 or more, or may be 0.0040 or more.
Note that the dielectric constant and dielectric loss tangent are values measured by the cavity resonator method as in the examples.
As described above, the resin composition, prepreg, laminate, and multilayer printed wiring board of the present invention can be suitably used for electronic equipment that handles high frequency signals of 1 GHz or more, and particularly for high frequency signals of 10 GHz or more or high frequency signals of 30 GHz or more. It can be suitably used in electronic equipment that handles signals.

[Laminated board, multilayer printed wiring board, and manufacturing method thereof]
The laminate of the present invention is a laminate containing the prepreg of the present invention and metal foil. The laminate of the present invention can be manufactured, for example, by laminating the prepreg obtained by the prepreg manufacturing method of the present invention and metal foil, and curing the prepreg by heating and pressurizing using a pressing method. More specifically, a metal plate is placed on one or both sides of one sheet of the prepreg of the present invention, or a metal foil is placed on one or both sides of a prepreg obtained by stacking two or more sheets of the prepreg of the present invention, and then heated. It can be manufactured by pressure molding.

The metal of the metal foil is not particularly limited as long as it is used for electrical insulating materials, but from the viewpoint of conductivity copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium , chromium, or an alloy containing at least one of these metal elements, preferably copper or aluminum, and preferably copper.

The conditions for heat and pressure molding are not particularly limited, but for example, it may be carried out at a temperature of 100 to 300°C, a pressure of 0.2 to 10.0 MPa, and a time of 0.1 to 5 hours. can. Further, the heating and pressure molding can be carried out by using a vacuum press or the like and maintaining a vacuum state for 0.5 to 5 hours.

Moreover, the multilayer printed wiring board of the present invention is a multilayer printed wiring board containing the prepreg or laminate of the present invention. That is, the multilayer printed wiring board of the present invention can be manufactured by heating and press-molding the prepreg or laminate of the present invention. The conditions for heating and pressure molding are not particularly limited, and the same conditions as above can be employed. The multilayer printed wiring board of the present invention can be obtained by, for example, applying a circuit forming process and a multilayer adhesive process to a prepreg obtained by the prepreg manufacturing method of the present invention or a laminate obtained by the laminate manufacturing method of the present invention. It can be manufactured by Examples of the circuit forming method include known methods, that is, circuit forming methods such as drilling, metal plating, and etching of metal foil.

[Semiconductor package]
The present invention also provides a semiconductor package including the printed wiring board, more specifically, a semiconductor package including a semiconductor element mounted on the printed wiring board. The semiconductor package of this embodiment can be manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position on the printed wiring board and sealing the semiconductor element with a sealing resin or the like.

Although the preferred embodiments of the present invention have been described above, these are merely examples for explaining the present invention, and are not intended to limit the scope of the present invention only to these embodiments.
The present invention can be implemented in various ways different from the above embodiments without departing from the spirit thereof.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to the following examples.

[Production of polyphenylene ether derivative (A)]
Polyphenylene ether derivative (A) was produced according to the following procedure and the blending amounts shown in Table 1.

(Production Example A-1: Production of polyphenylene ether derivative (A-1))
Toluene, polyphenylene ether with a number average molecular weight of about 16,000, and p-aminophenol were charged into a 2 L glass flask container equipped with a thermometer, a reflux condenser, and a stirrer that can be heated and cooled, and the mixture was heated to 90°C. Dissolved while stirring.
After visually confirming that it had dissolved, t-butylperoxyisopropyl monocarbonate and manganese naphthenate were added, and the solution was reacted at 90°C for 4 hours, then cooled to 70°C to form a primary amino group at the end of the molecule. A polyphenylene ether compound (A'') having the following was obtained.
When a small amount of this reaction solution was taken out and measured by gel permeation chromatography (GPC), the peak derived from p-aminophenol disappeared, and the number average molecular weight of the polyphenylene ether compound (A'') was approximately It was 9,200. In addition, a small amount of the reaction solution taken out was dropped into a methanol/benzene mixed solvent (mixed mass ratio: 1/1), and FT-IR measurement of the purified solid content (reaction product) by reprecipitation was performed. The appearance of a peak derived from a primary amino group near 400 cm ⁻¹ was confirmed.

Here, the number average molecular weight was calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is based on standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, Product name] was approximated by a cubic equation. GPC measurement conditions are shown below.
Device:
Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Column: Guard column; TSK Guardcolumn HHR-L+ column; TSKgel G4000HHR+TSKgel G2000HHR [all manufactured by Tosoh Corporation, product name]
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 30mg/5mL
Injection volume: 20μL
Flow rate: 1.00mL/min Measurement temperature: 40℃

Next, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (BMI-5100 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) and propylene glycol monomethyl were added to the above reaction solution. Add ether, raise the temperature of the liquid while stirring, react for 4 hours while keeping the temperature at 120°C, cool it, and filter through a 200 mesh filter to obtain polyphenylene ether derivative (A-1). Manufactured.

A small amount ^of this reaction solution was taken out and reprecipitated in the same manner as above, and FT-IR measurement of the purified solid was performed. The appearance of a peak derived from the carbonyl group of maleimide at , 730 cm ^-1 was confirmed. Further, when this solid was measured by GPC (same conditions as above), the number average molecular weight was about 9,400.

(Production Examples A-2 to A-3: Production of polyphenylene ether derivatives (A-2) to (A-3))
Polyphenylene ether derivatives (A-2) to (A-3) were produced in the same manner as Production Example A-1, except that the raw materials and blending amounts were changed as shown in Table 1. did. Table 1 shows the number average molecular weights of the polyphenylene ether derivatives (A-2) to (A-3).

The abbreviations of each material in Table 1 are as follows.
(1) Polyphenylene ether/PPO640: Polyphenylene ether, number average molecular weight = approximately 16,000, trade name (manufactured by SABIC Innovative Plastics)
(2) Aminophenol compound (VIII)
・p-aminophenol: manufactured by Ihara Chemical Industry Co., Ltd. ・m-aminophenol: manufactured by Kanto Chemical Co., Ltd. (3) Bismaleimide compound (IX)
・BMI-5100: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, trade name (manufactured by Daiwa Chemical Industries, Ltd.)
・BMI-4000: 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
・BMI-TMH: 1,6-bismaleimide-(2,2,4-trimethyl)hexane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
(4) Reaction catalyst/Perbutyl (registered trademark) I: t-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation)
・Manganese naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.)
(5) Organic solvent/toluene (manufactured by Kanto Kagaku Co., Ltd.)
・Propylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.)

[Production of aminobismaleimide compounds (C-1) to (C-3) and phenol-modified cyanate prepolymer (C-4)]
According to the following procedure and the blending amounts in Table 2, thermosetting resins, aminobismaleimide compounds (C-1) to (C-3) and a phenol-modified cyanate prepolymer (C-4) were produced.

[Production Example C-1: Production of aminobismaleimide compound (C-1)]
2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis( Add 4-(4-aminophenoxy)phenyl)propane and propylene glycol monomethyl ether, keep the liquid temperature at 120°C and react for 3 hours with stirring, then cool and filter through a 200 mesh filter. In this way, aminobismaleimide compound (C-1) was produced.

[Production Examples C-2 to C-3: Production of aminobismaleimide compounds (C-2) to (C-3)]
In Production Example C-1, aminobismaleimide compounds (C-2) to (C-3) were produced in the same manner as Production Example C-1, except that each raw material and its blending amount were changed as shown in Table 2. was manufactured.

[Production Example C-4: Production of phenol-modified cyanate prepolymer (C-4)]
Toluene, 2,2-bis(4-cyanatophenyl)propane, and p-(α-cumyl)phenol were placed in a 1 L glass flask equipped with a thermometer, reflux condenser, and stirrer that can be heated and cooled. After visually confirming that the solution had been dissolved, manganese naphthenate was added as a reaction catalyst with stirring while maintaining the liquid temperature at 110° C., and the reaction was allowed to proceed for 3 hours. Thereafter, the mixture was cooled and filtered through a 200 mesh filter to produce a phenol-modified cyanate prepolymer (C-4).

The abbreviations of each material in Table 2 are as follows.
(1) Maleimide compound (a)
・BMI-5100: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
・BMI-4000: 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
(2) Aromatic diamine compound (b)
・BAPP: 2,2-bis(4-(4-aminophenoxy)phenyl)propane, trade name (manufactured by Wakayama Seika Kogyo Co., Ltd.)
・Bisaniline-P: 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, trade name (manufactured by Mitsui Chemicals, Inc.)
・Bisaniline-M: 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, trade name (manufactured by Mitsui Chemicals, Inc.)
(3) Cyanate resin/BADCy: Primaset (registered trademark) BADCy, 2,2-bis(4-cyanatophenyl)propane (manufactured by Lonza)
(4) Monophenol compound/p-(α-cumyl)phenol (manufactured by Mitsui Chemicals Fine Co., Ltd.)
(5) Reaction catalyst: manganese naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.)
(6) Organic solvent/toluene (manufactured by Kanto Kagaku Co., Ltd.)
・Propylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.)

[Examples 1 to 21, Comparative Examples 1 to 17; Preparation of resin composition]
The ingredients listed in Tables 3 and 4 were stirred and mixed while heating at room temperature or 50 to 80°C according to the blending amounts (unit: parts by mass) listed in Tables 3 and 4. A resin composition having the solid content concentration shown was prepared.
Here, the blending amount of the inorganic filler is usually such that the density of the resin composition (excluding the inorganic filler) is 1.20 to 1.25 g/cm ³ , and the density of the inorganic filler used is 2. Since it is 2 to 3.01 g/cm ³ , when 160 parts by mass of the inorganic filler is blended with respect to 100 parts by mass of the resin composition (excluding the inorganic filler), the amount is about 39 to 48% by volume.
It should be noted that the raw materials and intermediate products used in the above production examples are in extremely small amounts or have been deactivated, and even if they remain in the resin composition, they can be ignored.

[Evaluation/measurement method]
Using the resin compositions obtained in Examples and Comparative Examples, prepregs and copper-clad laminates were produced according to the following methods, and each measurement and evaluation was performed using them. The results are shown in Tables 5 and 6. Note that the results of Examples 1 to 21 and Comparative Examples 1 to 17 in Tables 5 to 6 are based on the measurements and evaluations of the compositions prepared in Preparation Examples 1 to 21 and Comparative Preparation Examples 1 to 17 in Tables 3 and 5, respectively. This is the result.

(Production of prepreg and copper clad laminate)
The resin composition obtained in each example was applied to a glass cloth (E glass, manufactured by Nittobo Co., Ltd.) with a thickness of 0.1 mm, and then heated and dried at 160°C for 7 minutes to reduce the resin composition content ( A prepreg containing approximately 54% by mass (including organic solvents) was produced.
Six sheets of these prepregs were stacked, and 18 μm thick low profile copper foil (FV-WS, M-side Rz: 1.5 μm, manufactured by Furukawa Electric Co., Ltd.) was placed above and below so that the M-sides were in contact with each other. A double-sided copper-clad laminate (thickness: 0.8 mm) was produced by heat-pressing molding at a temperature of 230° C., a pressure of 3.9 MPa, and a time of 180 minutes.

(Appearance evaluation of prepreg)
The appearance of the prepreg obtained above was observed. The appearance was visually evaluated and evaluated according to the following criteria.
A: There is no abnormality in appearance.
C: There are some unevenness, streaks, foaming, phase separation, etc. on the surface of the prepreg, and the surface lacks smoothness.

(Measurement of prepreg outgas amount)
First, the mass of the prepreg (prepreg before heat treatment) produced in each example was measured. Next, the mass of the prepreg after heat-treating the prepreg at a temperature of 163° C. for 15 minutes (heat-treated prepreg) was measured. From these measured values, the amount of outgas of the prepreg was calculated using the following formula.
Outgas amount (mass%) = {(mass of prepreg before heat treatment - mass of prepreg after heat treatment) / mass of prepreg before heat treatment} x 100

(Characteristics evaluation of copper-clad laminates)
The copper-clad laminate obtained above was evaluated for high frequency characteristics, copper foil peel strength, glass transition temperature, coefficient of thermal expansion, solder heat resistance, and flame retardancy. The method for evaluating the characteristics of the copper-clad laminate is as follows.

(1) High-frequency characteristics After removing the copper foil on both sides of the copper-clad laminate by etching, the test piece was cut into a size of 60 mm x 2 mm and dried at 105°C/hr, and the Dk and Df at 10 GHz were measured. was calculated from the resonance frequency obtained by the cavity resonator method and the no-load Q value.
The measurement was carried out at an ambient temperature of 25° C. using vector network analyzer E8364B manufactured by Agilent Technologies, CP531 (10 GHz resonator) and CPMA-V2 (program) manufactured by Kanto Denshi Application Development Co., Ltd. as measuring instruments.
(2) Copper foil peeling strength Adhesion to conductor was measured in accordance with JIS C6481 (1996).
(3) Soldering heat resistance (moisture absorption heat resistance)
Using a 50 mm square test piece with etched copper foil on both sides of a copper-clad laminate, it was tested for a predetermined period of time (1 hour, After 3 hours and 5 hours) treatment, the test pieces were immersed in molten solder at 288° C. for 20 seconds, and the appearance of the test pieces after being immersed in solder was visually observed. Note that the numbers in the table mean the number of test pieces in which no abnormality such as blistering or measling was observed among the three test pieces after being immersed in solder.
(4) Glass transition temperature (Tg) and thermal expansion coefficient Glass transition temperature (Tg) and thermal expansion coefficient (plate thickness direction [Z direction], temperature range: 30 to 150°C) are 5 mm with copper foil etched on both sides. Using a corner test piece, a thermomechanical measuring device (TMA) [manufactured by TA Instruments Japan Co., Ltd., Q400 (model number)] was used to comply with IPC (The Institute for Interconnecting and Packaging Electronic Circuits) standards. The glass transition temperature and coefficient of thermal expansion (coefficient of linear expansion) were measured.
(5) Flame retardancy An evaluation board with a length of 127 mm and a width of 12 A .7 mm test piece was cut out, and flame retardancy was tested and evaluated using the test piece according to the UL94 test method (V method).
That is, a 20 mm flame was applied twice for 10 seconds to the lower end of the test piece held vertically. The evaluation was performed according to the standards of UL94 V method.

The abbreviations of each material in Tables 4 and 5 are as follows.
(1) Polyphenylene ether derivative/A-1: The polyphenylene ether derivative (A-1) obtained in Production Example (A-1) is prepared by removing the organic solvent or adding toluene and propylene glycol monomethyl ether. The solid content concentration specified in the table is as follows.
・A-2: The polyphenylene ether derivative (A-2) obtained in Production Example (A-2) is made into the solids listed in the table by removing the organic solvent or adding toluene and propylene glycol monomethyl ether as appropriate. Minute concentration.
・A-3: The polyphenylene ether derivative (A-3) obtained in Production Example (A-3) is converted into the solid shown in the table by removing the organic solvent or adding toluene and propylene glycol monomethyl ether as appropriate. Minute concentration.

(2) Curing accelerator (B)
<Organized oxide>
・Perbutyl (registered trademark) P: α,α'-bis(t-butylperoxy)diisopropylbenzene, trade name (manufactured by NOF Corporation), 1 minute half-life temperature 175.4°C
・Percmil (registered trademark) D: Bis(1-phenyl-1-methylethyl) peroxide, trade name (manufactured by NOF Corporation), 1 minute half-life temperature 175.2°C
・Percmil (registered trademark) P: diisopropylbenzene hydroperoxide, trade name (manufactured by NOF Corporation), 1 minute half-life temperature 232.5°C
<Imidazole curing agent>
・G-8009L: Isocyanate mask imidazole (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole), product name (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
・2MZ-H: 2-methylimidazole, trade name (manufactured by Shikoku Kasei Co., Ltd.)
・2E4MZ: 2-ethyl-4-methylimidazole, trade name (manufactured by Shikoku Kasei Co., Ltd.)
・1B2MZ: 1-benzyl-2-methylimidazole, trade name (manufactured by Shikoku Kasei Co., Ltd.) ・C11Z: 2-undecylimidazole, trade name (manufactured by Shikoku Kasei Co., Ltd.)
・2MA-OK: 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, trade name (manufactured by Shikoku Kasei Co., Ltd.)
<Phosphorous curing accelerator>
・TPP-MK: Tetotaphenylphosphonium, trade name (manufactured by Hokuko Sangyo Co., Ltd.)
・TPP-S: Triphenylphosphonium, trade name (manufactured by Hokuko Sangyo Co., Ltd.)

(3) Thermosetting resin (C)
・C-1: The amino bismaleimide compound (C-1) obtained in Production Example (C-1) is adjusted to the solid content listed in the table by removing the organic solvent or adding propylene glycol monomethyl ether as appropriate. Concentration.
・C-2: The aminobismaleimide compound (C-2) obtained in Production Example (C-2) is adjusted to the solid content listed in the table by removing the organic solvent or adding propylene glycol monomethyl ether as appropriate. Concentration.
・C-3: The amino bismaleimide compound (C-3) obtained in Production Example (C-3) is adjusted to the solid content listed in the table by removing the organic solvent or adding propylene glycol monomethyl ether as appropriate. Concentration.
・C-4: The phenol-modified cyanate prepolymer (C-4) obtained in Production Example (C-4) was adjusted to the solid content concentration listed in the table by removing the organic solvent or adding toluene as appropriate. What I did.
・NC-7000L: Naphthol novolac type epoxy resin, trade name (manufactured by Nippon Kayaku Co., Ltd.)

(4) Inorganic filler (D)
・SO-C2: Spherical fused silica, average particle size: 0.5 μm, density 2.2 g/cm ³ , product name (manufactured by Admatex Co., Ltd.)

(5) Flame retardant (E)
・OP-930: Dialkyl phosphinic acid aluminum salt, metal salt of disubstituted phosphinic acid, phosphorus content: 23.5% by mass, trade name (manufactured by Clariant)
・HCA-HQ: 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, cyclic organic phosphorus compound, phosphorus content: 9.6% by mass , Product name (manufactured by Sanko Co., Ltd.)

Examples 1 to 16 are resins containing a polyphenylene ether derivative (A) and at least one curing accelerator (B) selected from the group consisting of an organic peroxide, an imidazole curing accelerator, and a phosphorus curing accelerator. This is an example using a composition.
Comparing the laminates according to Examples 1 to 12 with Comparative Examples 1 to 12 described later, it is found that they have excellent high frequency characteristics (particularly dielectric loss tangent at 10 GHz), as well as excellent moisture absorption and heat resistance, adhesion with conductors, and glass transition. It has a good balance of temperature, thermal expansion characteristics, and flame retardancy. In particular, it can be seen that the high frequency characteristics were influenced by the solid content concentration in the resin composition.

Examples 17 to 21 are examples in which resin compositions containing the polyphenylene ether derivative (A) and not containing the curing accelerator (B) were used. Comparing Examples 17 to 21 with Comparative Examples 13 to 17, it can be seen that they are excellent in high frequency characteristics (particularly dielectric loss tangent at 10 GHz) and are affected by the solid content concentration in the resin composition.

The prepreg and resin composition of the present invention have high adhesion to conductors, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion and flame retardancy, as well as stable and excellent high frequency properties (in high frequency bands). dielectric properties). The prepreg and the laminate containing the prepreg can be suitably used for electronic component applications such as multilayer printed wiring boards and semiconductor packages.

Claims (19)

A prepreg comprising a resin composition and a sheet-like fiber reinforced base material,
A prepreg in which the amount of outgas generated when heated at a temperature of 163° C. for 15 minutes is less than 0.7% by mass based on the entire prepreg. The prepreg according to claim 1, wherein the resin composition contains a polyphenylene ether derivative (A) having an N-substituted maleimide structure-containing group. The prepreg according to claim 2, wherein the N-substituted maleimide structure-containing group is a group containing a bismaleimide structure in which nitrogen atoms of two maleimide groups are bonded to each other via an organic group. The prepreg according to claim 2 or 3, wherein the N-substituted maleimide structure-containing group is a group represented by the following general formula (Z).

(In the formula, each R ² is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. y is an integer of 0 to 4. ^{A 1} is represented by the following general formula (II), ( III), (IV) or (V).)

(In the formula, each R ³ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p is an integer of 0 to 4.)

(In the formula, R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 2} is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, single bond, or a group represented by the following general formula (III-1).q and r are each independently an integer of 0 to 4. be.)

(In the formula, R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 3} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. s and t are each independently an integer of 0 to 4.)

(In the formula, n is an integer from 0 to 10.)

(In the formula, R ⁸ and R ⁹ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u is an integer of 1 to 8.) Any one of claims 1 to 4, wherein the resin composition further contains at least one curing accelerator (B) selected from the group consisting of organic peroxides, imidazole curing accelerators, and phosphorus curing accelerators. Prepreg according to item 1. The prepreg according to any one of claims 1 to 5, wherein the resin composition further contains at least one thermosetting resin (C) selected from the group consisting of an epoxy resin, a cyanate resin, and a maleimide compound. The maleimide compound in the thermosetting resin (C) is a maleimide compound (a) having at least two N-substituted maleimide structure-containing groups, and an aminobismaleimide compound (c) represented by the following general formula (VI). The prepreg according to claim 6, comprising at least one member selected from the group consisting of:

(In the formula, ^A4 is the same as the definition of ^A1 in the general formula (Z) described in claim 4, and ^A5 is a group represented by the following general formula (VII).)

(In the formula, R ¹⁷ and R ¹⁸ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. ^{A 8} is an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. 5 alkylene group, alkylidene group having 2 to 5 carbon atoms, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, fluorenylene group, single bond, or the following general formula (VII-1) or (VII-2) ). q' and r' are each independently an integer of 0 to 4.)

(In the formula, R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 9} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- or p-phenylene diisopropylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, or single bond. s' and t' are each independently an integer of 0 to 4.)

(In the formula, R ²¹ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹⁰ and A ¹¹ are each independently an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. w is an integer from 0 to 4.) A laminate comprising the prepreg according to any one of claims 1 to 7 and metal foil. A multilayer printed wiring board comprising the prepreg according to any one of claims 1 to 7 or the laminate according to claim 8. A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to claim 9. A resin composition containing a polyphenylene ether derivative (A) having an N-substituted maleimide structure-containing group and an organic solvent, and having a solid content concentration of 50.5% by mass or more. The resin composition according to claim 11, wherein the polyphenylene ether derivative (A) having an N-substituted maleimide structure-containing group has a structural unit represented by the following general formula (I).

(In the formula, each R ¹ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. x is an integer of 0 to 4.) The resin composition according to claim 11 or 12, wherein the N-substituted maleimide structure-containing group is a group represented by the following general formula (Z).

(In the formula, R ² is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. y is an integer of 0 to 4. ^{A 1} is represented by the following general formula (II), ( III), (IV) or (V).)

(In the formula, each R ³ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p is an integer of 0 to 4.)

(In the formula, R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 2} is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, single bond, or a group represented by the following general formula (III-1).q and r are each independently an integer of 0 to 4. be.)

(In the formula, R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 3} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. s and t are each independently an integer of 0 to 4.)

(In the formula, n is an integer from 0 to 10.)

(In the formula, R ⁸ and R ⁹ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u is an integer of 1 to 8.) The resin according to any one of claims 11 to 13, further comprising at least one curing accelerator (B) selected from the group consisting of organic peroxides, imidazole-based curing accelerators, and phosphorus-based curing accelerators. Composition. The resin composition according to any one of claims 11 to 14, further comprising at least one thermosetting resin (C) selected from the group consisting of epoxy resins, cyanate resins, and maleimide compounds. The maleimide compound in the thermosetting resin (C) is a maleimide compound (a) having at least two N-substituted maleimide structure-containing groups, and an aminobismaleimide compound (c) represented by the following general formula (VI). The resin composition according to claim 15, comprising at least one selected from the group consisting of.

(In the formula, A ⁴ is the same as the definition of A ¹ in the general formula (Z) described in claim 13, and A ⁵ is a group represented by the following general formula (VII).)

(In the formula, R ¹⁷ and R ¹⁸ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. ^{A 8} is an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. 5 alkylene group, alkylidene group having 2 to 5 carbon atoms, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, fluorenylene group, single bond, or the following general formula (VII-1) or (VII-2) ). q' and r' are each independently an integer of 0 to 4.)

(In the formula, R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. ^{A 9} is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- or p-phenylene diisopropylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, or single bond. s' and t' are each independently an integer of 0 to 4.)

(In the formula, R ²¹ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹⁰ and A ¹¹ are each independently an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. w is an integer from 0 to 4.) A prepreg production method in which a prepreg is produced by impregnating or coating a sheet-like fiber-reinforced base material with a resin composition and drying it, comprising a step (X) of treating the prepreg so that the amount of outgas of the prepreg satisfies the following conditions. A method for producing prepreg, including:
(Condition of outgas amount)
The amount of outgas generated when heated at a temperature of 163° C. for 15 minutes is less than 0.7% by mass based on the entire prepreg. A method for producing a laminate, comprising laminating a prepreg obtained by the method for producing a prepreg according to claim 17 and a metal foil, and heating and pressurizing the prepreg by a pressing method. A multilayer printed wiring board obtained by subjecting a prepreg obtained by the method for producing a prepreg according to claim 17 or a laminate obtained by the method for producing a laminate according to claim 18 to circuit formation processing and multilayer adhesive processing. manufacturing method.